Integration of electrochromic films on a substrate

ABSTRACT

The present disclosure relates generally to methods for the integration of electrochromic films onto a substrate, such as a glass window, and the systems/structures formed via such methods.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.16/441,408, filed Jun. 14, 2019, now allowed, which is a continuation ofU.S. application Ser. No. 15/399,852, filed Jan. 6, 2017, now U.S. Pat.No. 10,392,301 B2, which is based on and claims priority to U.S.Provisional Application No. 62/349,841, filed Jun. 14, 2016, entitled“Integration of Electrochromic Films on a Substrate,” and 62/323,407,filed Apr. 15, 2016, titled “Solid Polymer Electrolyte forElectrochromic Devices.” The entire contents of the above-referencedapplications are all incorporated herein by reference.

FIELD OF THE INVENTION

The invention generally relates to methods for the integration ofelectrochromic films, which comprise a solid state electrolyte disposedtherein, on a substrate, and the resulting systems/structures.

BACKGROUND

Electrochromism generally refers to a reversible change in opticalproperties of a material upon application of a potential. In particular,electrochromic materials exhibit a reversible color change due to anelectrochemical reduction-oxidation (redox) reaction caused byapplication of an electric field.

Electrochromic materials are useful for a variety of applications,including photovoltaic devices, field effect transistors, organic lightemitting diodes, general printed electronics, anti-glare window anddisplay systems, etc. For applications involving smart windowtechnology, the electrochromic materials need to be integrated with aglass substrate (e.g., a glass window) to become serviceable.

There is a thus a need to develop new and/or improved structuresintegrating electrochromic materials with desired substrates (e.g.,glass). Likewise, there is also a need to develop new and/or improvedmethods of integrating electrochromic materials with a desired substratethat involve cost effective, efficient, and reproducible processes.

BRIEF SUMMARY

The present disclosure provides unique methods for the integration offlexible electrochromic films comprising a solid state electrolytedisposed therein onto a desired substrate (e.g., a glass window). Thepresent disclosure additionally describes the unique systems/structuresformed via such methods.

In one embodiment, a method for directly applying an electrochromic filmto a surface of a substrate is provided, where the electrochromic filmcomprises a solid state electrolyte disposed therein, and where themethod comprises: selecting an electrochromic film having at least oneadhesive surface configured to adhere to a surface of a substrate,wherein the electrochromic film comprises an additional layer coupled tothe adhesive surface; removing the additional layer from theelectrochromic film to expose the adhesive surface; and contacting theexposed adhesive surface of the electrochromic film directly to thesurface of the substrate to apply the electrochromic film thereto.

In another embodiment, a method for forming a structure having anelectrochromic film comprising a solid state electrolyte disposedtherein is provided, where the method comprises: interposing anelectrochromic film between a first adhesive interlayer and a secondadhesive interlayer, wherein the first adhesive interlayer is interposedbetween the electrochromic film and a first substrate, and the secondadhesive interlayer is interposed between the electrochromic film and asecond substrate; and bonding the electrochromic film to the firstsubstrate via the first adhesive interlayer, and to the second substratevia the second adhesive interlayer, to form a laminated structure havingthe electrochromic film therein.

In yet another embodiment, a structure comprising at least oneelectrochromic film comprising a solid state electrolyte disposedtherein is provided, where the method comprises: a first panel having afirst surface and a second surface; a second panel having a thirdsurface and a fourth surface, the third surface of the second panelfacing toward the second surface of the first panel; and a spacerinterposed between the first panel and the second panel. Alow-emissivity coating is deposited on at least one of the secondsurface of the first panel and the third surface of the second panel. Anelectrochromic film comprising a solid state electrolyte therein isdeposited on at least one of the first surface of the first panel, thesecond surface of the first panel, the third surface of the secondpanel, and the fourth surface of the second panel, with the proviso thatthe electrochromic film and the low-emissivity coating are not depositedon a same surface at a same time.

In a further embodiment, a structure comprising at least one laminatedstructure having an electrochromic film disposed therein is provided,where the electrochromic film comprises a solid state electrolytedisposed therein, and where the structure comprises: a first panelhaving a first surface and a second surface; a second panel having athird surface and a fourth surface, the third surface of the secondpanel facing toward the second surface of the first panel; and a spacerinterposed between the first panel and the second panel. Alow-emissivity coating is deposited on at least one of the secondsurface of the first panel, and the third surface of the second panel.At least one of the first panel and the second panel comprises alaminated structure having an electrochromic film disposed therein.

In an additional embodiment, a multi-panel structure having anelectrochromic film associated with at least one of the panels isprovided, where the electrochromic film comprises a solid stateelectrolyte disposed therein, and where the multi-panel structurecomprises: a first panel having a first surface and a second surface; asecond panel having a third surface and a fourth surface; and a centralpanel interposed between the first panel and the second panel, thecentral panel having a fifth surface facing toward the second surface ofthe first panel, and a sixth surface facing toward the third surface ofthe second panel. The first panel, the second panel and the centralpanel are in spaced relation with each other. A low-emissivity coatingis deposited on at least one of the second surface of the first paneland the third surface of the second panel. An electrochromic filmcomprising a solid state electrolyte disposed therein is also associatedwith the central panel.

Other objects, features and advantages of the described embodiments willbecome apparent to those skilled in the art from the following detaileddescription. It is to be understood, however, that the detaileddescription and specific examples, while indicating exemplaryembodiments of the present invention, are given by way of illustrationand not limitation. Many changes and modifications within the scope ofthe present invention may be made without departing from the spiritthereof, and the invention includes all such modifications.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred and non-limiting embodiments of the invention may be morereadily understood by referring to the accompanying drawings in which:

FIG. 1 is a flowchart of a method for laminating an electrochromic filmon a substrate, where the electrochromic film comprises a solid stateelectrolyte disposed therein, according to one exemplary embodiment.

FIG. 2 is a simplified schematic of a substrate on which anelectrochromic film is directly laminated, where the electrochromic filmcomprises a solid state electrolyte disposed therein, according to oneexemplary embodiment.

FIG. 3 is a flowchart of a method for interposing an electrochromic filmwithin a laminated structure, where the electrochromic film comprises asolid state electrolyte disposed therein, according to one exemplary.

FIG. 4 is a simplified schematic of a laminated structure, according toone exemplary embodiment.

FIG. 5 is a simplified schematic of a laminated structure having anelectrochromic film disposed therein, where the electrochromic filmcomprises a solid state electrolyte disposed therein, according to oneexemplary embodiment.

FIG. 6 is a flowchart of a method for forming a module comprising alaminated structure with an electrochromic film, where theelectrochromic film comprises a solid state electrolyte disposedtherein, according to one exemplary embodiment.

FIG. 7 is a simplified schematic of a module comprising a laminatedstructure with an electrochromic film disposed therein, where theelectrochromic film comprises a solid state electrolyte disposedtherein, according to one exemplary embodiment.

FIG. 8 is a simplified schematic of an exterior window structure havingthe module of FIG. 7 integrated therewith, according to one exemplaryembodiment.

FIG. 9 is a simplified schematic of a double glazing structure havingtwo panels and a low-emissivity coating deposited on at least onesurface of at least one of the panels, according to one exemplaryembodiment.

FIGS. 10A-10F are cross sectional views of a double glazinglow-emissivity structure having two panels, at least one of whichcomprises a laminated structure having an electrochromic film disposedtherein, where the electrochromic film comprises a solid stateelectrolyte disposed therein, according to various exemplaryembodiments.

FIGS. 11A-11H illustrate cross-sectional views of a double glazinglow-emissivity structure having two panel, at least one of whichcomprises a laminated structure having an electrochromic film disposedtherein, where the electrochromic film comprises a solid stateelectrolyte disposed therein, according to various exemplaryembodiments.

FIG. 12 is a simplified schematic of a double glazing low emissivitystructure having at least three panels in spaced relation with eachother, where at least one of the panels comprises an electrochromic filmassociated therewith, where the electrochromic film comprises a solidstate electrolyte disposed therein, according to one exemplaryembodiment.

FIG. 13 is a simplified schematic of an electrochromic film comprising asolid state electrolyte disposed therein, according to one exemplaryembodiment.

FIG. 14 is a simplified schematic of an electrochromic film directlylaminated on a glass substrate, where the electrochromic film comprisesa solid state electrolyte disposed therein, according to one exemplaryembodiment.

FIG. 15 is simplified schematic of a laminated glass structure with anelectrochromic film disposed therein, where the electrochromic filmcomprises a solid state electrolyte disposed therein, according to oneexemplary embodiment.

FIGS. 16A-16B are simplified schematics of a smart window module in atransparent state and an opaque state, respectively, where the smartwindow module comprises a laminated glass structure with anelectrochromic film disposed therein, and where the electrochromic filmcomprises a solid state electrolyte disposed therein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various embodiments of theinvention. However, one skilled in the art will understand that theinvention may be practiced without these details. Moreover, whilevarious embodiments of the invention are disclosed herein, manyadaptations and modifications may be made within the scope of theinvention in accordance with the common general knowledge of thoseskilled in this art. Such modifications include the substitution ofknown equivalents for any aspect of the invention in order to achievethe same result in substantially the same way.

Unless the context requires otherwise, throughout the presentspecification and claims, the word “comprise” and variations thereof,such as, “comprises” and “comprising” are to be construed in an open,inclusive sense, that is as “including, but not limited to.” Recitationof numeric ranges of values throughout the specification is intended toserve as a shorthand notation of referring individually to each separatevalue falling within the range inclusive of the values defining therange, and each separate value is incorporated in the specification asit were individually recited herein. Additionally, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment of the present invention. Thus, the appearances of thephrases “in one embodiment” or “in an embodiment” in various placesthroughout this specification are not necessarily all referring to thesame embodiment, but may be in some instances. Furthermore, theparticular features, structures, or characteristics may be combined inany suitable manner in one or more embodiments.

Lamination of an Electrochromic Film on a Substrate

FIG. 1 illustrates a flowchart of a method 100 for laminating anelectrochromic film on a substrate, where the electrochromic filmcomprises a solid state electrolyte therein, according to one exemplaryembodiment. The method 100 may be implemented to construct any of thestructures/components/devices described herein, such as those describedwith reference to other embodiments and/or FIGS. The method 100 may becarried out in any desired environment, and may include more or lesssteps than those described and/or illustrated in FIG. 1 .

As shown in FIG. 1 , the method 100 may include selecting anelectrochromic film having a solid state electrolyte disposed therein(included within/inside the electrochromic film), and at least oneadhesive surface configured to adhere to a surface of a substrate. Seestep 102. The electrochromic film may also include an additional layer,e.g., a liner, coupled to the adhesive surface thereof. This additionallayer coupled to, and covering at least a portion, a majority, orpreferably an entirety of the adhesive surface of the electrochromicfilm, may help prevent the electrochromic film from adhering toundesired/unintended surfaces, as well as prematurely adhering to thedesired/intended surface of the substrate.

Selection of the electrochromic film may include first measuring thesubstrate to determine the dimensions thereof, and selecting and/orfabricating an electrochromic film with at least one dimensionequivalent and/or substantially complementary to the correspondingdimensions of the substrate. In certain embodiments, the dimensions(e.g., width, height, etc.) of the selected electrochromic film may beabout equal to the corresponding dimensions of the substrate such thatthe electrochromic film, when adhered to the substrate surface, maycover the entirety thereof. In certain embodiments, at least one of thedimensions (e.g., width, height, etc.) of the selected electrochromicfilm may be less than the corresponding dimension(s) of the substratesuch that the electrochromic film, when adhered to the substratesurface, may cover less than an entirety thereof (e.g., only a portionof the substrate surface). In certain embodiments, at least one of thedimensions (e.g., width, height, etc.) of the selected electrochromicfilm may be greater than the corresponding dimension(s) of the substratesuch that the electrochromic film, when adhered to the substratesurface, may not only cover the entirety thereof, but also have one ormore portions that overhang (extend beyond) the perimeter of thesubstrate surface. In such embodiments where at least one of thedimensions (e.g., width, height, etc.) of the selected electrochromicfilm are greater than the corresponding dimension(s) of the substrate,additional processing steps may be required to remove the overhangingportion(s) of the electrochromic film (the portion(s) of theelectrochromic film not adhered to the substrate's surface).

In certain embodiments, the substrate may comprise a transparentmaterial. In one embodiment, the substrate may be a transparent glasssubstrate. In a particular embodiment, the substrate may be atransparent glass window.

In some embodiments, the substrate may comprise a rigid (non-pliant)material; a semi-rigid (semi-pliant) material; a pliant/flexiblematerial, and combinations thereof. A flexible substrate may bebeneficial in terms of weight, ease of transportation, etc., in certainembodiments.

In various embodiments, the surface of the substrate to which theelectrochromic film will adhere may be substantially flat, comprise oneor more curved portions, or have any desiredconfiguration/shape/dimensions as would be appreciated by skilledartisans upon reading the present disclosure.

As also shown in FIG. 1 , the method 100 includes preparation of thesurface of the substrate to which the electrochromic film will adhere.See step 104. In some embodiments, such preparation may include cleaningthe substrate surface via one or more processes as would be appreciatedby skilled artisans upon reading the present disclosure. As used herein,the term “adhere” refers to the state in which two surfaces are held,bonded, or otherwise coupled together.

The method 100 further includes removing the additional layer from theelectrochromic film to expose the adhesive surface thereof. See step106. After removal of the additional layer from the electrochromic film,the method 100 may optionally include wetting (e.g., applying apredetermined amount of a fluid, such as water or an aqueous fluid) theexposed adhesive surface. See step 108.

As additionally shown in FIG. 1 , the method 100 includes contacting theexposed adhesive surface of the electrochromic film to the substratesurface, thereby laminating/adhering the electrochromic film to thesubstrate surface. See step 110. In preferred embodiments, the method100 results in laminating/adhering the electrochromic film directly onthe substrate surface.

While not shown in FIG. 1 , the method 100 may include one or moreprocessing steps, including, but not limited to, applying pressure tothe electrochromic film laminated on the substrate, wetting theelectrochromic film (e.g., via a squeegee) laminated on the substrate,and subsequently drying the electrochromic film laminated on thesubstrate, etc.

A simplified schematic of a structure comprising an electrochromic filmlaminated directly on a substrate is shown in FIG. 2 , according to oneexemplary embodiment. For clarity purposes only, the various componentsof the structure (e.g., the electrochromic film and substrate) are shownspaced apart. Moreover, while not shown in FIG. 2 , the electrochromicfilm may comprise a solid state electrolyte disposed therein.

As shown in FIG. 2 , the structure 200 comprises a substrate 202 (e.g.,glass) having a first surface 204 to which the electrochromic film 206adheres. The electrochromic film 206 has an adhesive surface 208, whichis coupled to an additional layer (not shown in FIG. 2 ) prior tolamination with the substrate 202. As indicated above,laminating/adhering the electrochromic film 206 to the first surface 204of the substrate 202 may include at least the steps of removing theadditional layer coupled to the adhesive surface 208 of theelectrochromic film 206, and contacting the adhesive surface 208directly to the first surface 204 of the substrate 202.

As shown in the embodiment of FIG. 2 , the substrate 202 and theelectrochromic film 206 have about an equal width, w, relative to oneanother, as well as about an equal height, h, relative to one another.

In certain embodiments the electrochromic film 206 may be applied andadhered to the first surface 204 of the substrate 202, or a secondsurface (e.g., surface 210) of the substrate 202. For instance, inembodiments where the substrate 202 may be a glass window, such as aglass window in a building, car, aircraft, etc., the surfaces 204, 210may correspond to an interior surface and an exterior surface of thewindow, respectively.

In some embodiments, the electrochromic film 206 may be applied andadhered to the first surface 204 of the substrate 202, and at least asecond electrochromic film may be applied and adhered to at least oneother surface of the substrate 202.

Interposition of an Electrochromic Film within a Laminated Structure

FIG. 3 illustrates a flowchart of a method 300 for interposing anelectrochromic film within a laminated structure, where theelectrochromic film comprises a solid state electrolyte disposedtherein, according to one exemplary embodiment. The method 300 may beimplemented to construct any of the structures/components/devicesdescribed herein, such as those described with reference to otherembodiments and/or FIGS. The method 300 may be carried out in anydesired environment, and may include more or less steps than thosedescribed and/or illustrated in FIG. 3 .

As shown in FIG. 3 , the method 300 includes interposing (e.g.,sandwiching) an electrochromic film between a first adhesive interlayerand a second adhesive interlayer. The first adhesive interlayer isinterposed between the electrochromic film and a first substrate, andthe second adhesive interlayer is interposed between the electrochromicfilm and a second substrate. See step 302. As indicated above, theelectrochromic film may comprise a solid state electrolyte disposedtherein in some embodiments.

In certain embodiments, the first adhesive interlayer and/or the secondadhesive interlayer may include a material configured to bond theelectrochromic film thereto. For instance, in one embodiment, the firstadhesive interlayer and/or the second adhesive interlayer may include apolymeric material, particularly a thermosetting polymer material.Suitable thermoset polymer materials may include, but are not limitedto, polyvinyl butyral (PVB), ethylene-vinyl acetate (EVA),polyurethanes, etc.

In certain embodiments, the first adhesive interlayer and/or the secondadhesive interlayer may comprise a material that not only is configuredto bond the electrochromic film thereto, but is also transparent.

In certain embodiments, the first substrate and/or the second substratemay comprise a transparent material. In one embodiment, the firstsubstrate and/or the second substrate may be transparent glass. In aparticular embodiment, the first substrate and/or the second substratemay be a transparent glass window.

In some embodiments, the first substrate and/or the second substrate maycomprise a rigid (non-pliant) material; a semi-rigid (semi-pliant)material; a pliant/flexible material, and combinations thereof.

In certain embodiments, the surface of the first substrate to which thefirst adhesive interlayer will bond may be substantially flat, compriseone or more curved portions, or have any desiredconfiguration/shape/dimensions as would be appreciated by skilledartisans upon reading the present disclosure. In certain embodiments,the surface of the second substrate to which the second adhesiveinterlayer will bond may be substantially flat, comprise one or morecurved portions, or have any desired configuration/shape/dimensions aswould be appreciated by skilled artisans upon reading the presentdisclosure.

In certain embodiments, the corresponding dimensions (e.g., width,height, etc.) of one or more of: the first adhesive interlayer, thesecond adhesive interlayer, the electrochromic film, the firstsubstrate, and the second substrate, may be about equal to one another.In one embodiment, the corresponding dimensions of each of: the firstadhesive interlayer, the second adhesive interlayer, the electrochromicfilm, the first substrate, and the second substrate, may be about equalto one another.

As also shown in FIG. 3 , the method 300 includes bonding theelectrochromic film to the first substrate via the first adhesiveinterlayer, and bonding the electrochromic film to the second substratevia the second adhesive interlayer. See step 302.

In certain embodiments where the first adhesive interlayer and/or thesecond adhesive interlayer comprises a thermosetting polymer material,the bonding step may involve applying heat and/or pressure and/or UVirradiation to cross-link the electrochromic film with the first andsecond substrates.

A simplified schematic of an exemplary laminated structure without anelectrochromic film therein is shown in FIG. 4 , according to oneexemplary embodiment. For clarity purposes only, the various componentsof the laminated structure (e.g., substrates, and adhesive interlayers)are shown spaced apart.

As shown in FIG. 4 , the laminated structure 400 is constructed in amanner that allows the structure 400 to stay together whenshattered/broken, thereby providing safety protection. For instance, thelaminated structure 400 comprises at least two substrates 402, 404(e.g., each comprising glass) bonded together via an adhesive interlayer406. The adhesive interlayer 406 is particularly configured to keep thesubstrates 402, 404 bonded together even when shattered/broken, wherethe high strength of the adhesive interlayer 406 prevents the substrates402, 404 from breaking up into large, sharp pieces.

A simplified schematic of a laminated structure with an electrochromicfilm interposed therein is shown in FIG. 5 , according to one exemplaryembodiment. For clarity purposes only, the various components of thelaminated structure (e.g., substrates, adhesive layers, andelectrochromic film) are shown spaced apart. Moreover, while not shownin FIG. 5 , the electrochromic film may comprise a solid stateelectrolyte disposed therein.

As shown in FIG. 5 , the laminated structure 500 includes a firstadhesive interlayer 502 interposed between a first surface 504 of anelectrochromic film 506 and a first substrate 508. The laminatedstructure 500 also includes a second adhesive interlayer 510 interposedbetween a second surface 512 of the electrochromic film 506 and a secondsubstrate 514. As seen in the embodiment of FIG. 5 , the first andsecond surfaces 504, 512 correspond to opposing surfaces of theelectrochromic film 506.

As indicated previously, the first and/or second adhesive interlayers502, 510 may include a material (e.g., a thermosetting polymer material)configured to securely bond (e.g., cross-link) the electrochromic film506 with the first and second substrates 508, 514. As such, the firstand/or second adhesive interlayers 502, 510 are configured to keep thelaminated structure 500 together even when shattered/broken, and preventthe laminated structure 500 from breaking up into large, sharp pieces.

As shown in the embodiment of FIG. 5 , the first substrate 508, thefirst adhesive interlayer 502, the electrochromic film 506, the secondadhesive interlayer 510, and the second substrate 514 may each haveabout an equal width, w, as one another, as well as about an equalheight, h, as one another; however, this need not be the case in otherembodiments.

In certain embodiments, the laminated structure 500 may be suitable foruse as an exterior window of a car, building, aircraft, etc. in certainembodiments. In some embodiments, such a laminated structure 500 may besuitable for use as a curtain wall.

Forming a Module Comprising an Electrochromic Film Disposed within aLaminated Structure

FIG. 6 illustrates a flowchart of a method 600 for forming a modulecomprising a laminated structure with an electrochromic film disposedtherein, where the electrochromic film comprises a solid stateelectrolyte disposed therein (i.e., the solid state electrolyte isdisposed/incorporated within/inside the electrochromic film), accordingto one exemplary embodiment. The method 600 may be implemented toconstruct any of the structures/components/devices described herein,such as those described with reference to other embodiments and/or FIGS.The method 600 may be carried out in any desired environment, and mayinclude more or less steps than those described and/or illustrated inFIG. 6 .

As shown in FIG. 6 , the method 600 includes forming a laminatedstructure having an electrochromic film disposed therein, wherein theelectrochromic film comprises a solid state electrolyte disposedtherein. See step 602. In certain embodiments, formation of such alaminated structure may proceed according to the method 300 described inFIG. 3 . For instance, formation of such a laminated structure mayinclude: (i) interposing an electrochromic film between a first adhesiveinterlayer and second adhesive interlayer, the first adhesive interlayerbeing interposed between the electrochromic film and a first substrate,and the second adhesive interlayer being interposed between theelectrochromic film and a second substrate; and (ii) bonding theelectrochromic film to the first substrate via the first adhesiveinterlayer, and to the second substrate via the second adhesiveinterlayer.

In certain embodiments, the first adhesive interlayer and/or the secondadhesive interlayers may include a polymeric material, particularly athermosetting polymer material (e.g., PVB, EVA, polyurethanes, etc.),configured to bond the electrochromic film to the first and secondsubstrates. In certain embodiments, the first adhesive interlayer and/orthe second adhesive interlayer may comprise a material that not only isconfigured to bond the electrochromic film to the first and secondsubstrates, but is also transparent.

In certain embodiments where the first adhesive interlayer and/or thesecond adhesive interlayer comprises a thermosetting polymer material,the bonding step may involve applying heat and/or pressure and/or UVirradiation to cross-link the electrochromic film with the first andsecond substrates.

In certain embodiments, the first substrate and/or the second substratemay comprise a transparent material. In one embodiment, the firstsubstrate and/or the second substrate may be transparent glass. Inparticular embodiments, the first substrate and/or the second substratemay be a transparent glass window.

In some embodiments, the first substrate and/or the second substrate maycomprise a rigid (non-pliant) material; a semi-rigid (semi-pliant)material; a pliant/flexible material, and combinations thereof.

In certain embodiments, the surface of the first substrate to which thefirst adhesive interlayer will bond may be substantially flat, compriseone or more curved portions, or have any desiredconfiguration/shape/dimensions as would be appreciated by skilledartisans upon reading the present disclosure. In certain embodiments,the surface of the substrate to which the second adhesive interlayerwill bond may be substantially flat, comprise one or more curvedportions, or have any desired configuration/shape/dimensions as would beappreciated by skilled artisans upon reading the present disclosure.

In certain embodiments, the corresponding dimensions (e.g., width,height, etc.) of one or more of: the first adhesive interlayer, thesecond adhesive interlayer, the electrochromic film, the firstsubstrate, and the second substrate, may be about equal to one another.In one embodiment, the corresponding dimensions of each of: the firstadhesive interlayer, the second adhesive interlayer, the electrochromicfilm, the first substrate, and the second substrate, may be about equalto one another.

As further shown in FIG. 6 , the method 600 includes attaching one ormore peripheral portions of the laminated structure having theelectrochromic film disposed therein to a support unit, thereby forminga module. See step 604. In certain embodiments, the one or moreperipheral portions of the laminated structure having the electrochromicfilm disposed therein may attach to an inner region of the support unit.Such attachment may be achieved by way of adhesives, rubber gaskets, orother suitable fastening device/structure as would be appreciated byskilled artisans upon reading the present disclosure.

In certain embodiments, the support unit may be a frame (e.g., a windowframe). In some embodiments, one or more electronic componentsconfigured to control operation of the electrochromic film may bedisposed within the support unit (e.g., within at least one wall of thesupport unit).

In certain embodiments, the resulting module having the electroniccomponent(s) associated therewith may be commercially available to anend user, and used for a variety of applications. For example, an enduser may install the resulting module having the electronic component(s)associated therewith as an interior window, e.g. as described in FIG. 8.

A simplified schematic of a module (e.g., a smart window module)comprising an electrochromic film disposed within a laminated structureis shown in FIG. 7 , according to one exemplary embodiment. For claritypurposes only, the various components of the module (e.g., support unit,substrates, adhesive interlayers, and electrochromic film) are shownspaced apart. Moreover, while not shown in FIG. 7 , the electrochromicfilm comprises a solid state disposed therein.

As shown in FIG. 7 , the module 700 includes a laminated structure 702with an electrochromic film 704 disposed therein. This laminatedstructure 702 particularly includes a first adhesive interlayer 706interposed between a first surface 708 of the electrochromic film 704and a first substrate 710. The laminated structure 702 also includes asecond adhesive interlayer 712 interposed between a second surface 714of the electrochromic film 704 and a second substrate 716. As seen inthe embodiment of FIG. 7 , the first and second surfaces 708, 714correspond to opposing surfaces of the electrochromic film 704. Incertain embodiments, the laminated structure 702 may be formed accordingto the method 300 of FIG. 3 , and have a similar, or the same,configuration and/or composition of the structure 500 of FIG. 5 .

The first and/or second adhesive interlayers 706, 712 of FIG. 7 mayinclude a material (e.g., a thermosetting polymer material) configuredto securely bond (e.g., cross-link) the electrochromic film 704 with thefirst and second substrates 710, 716. As such, the first and/or secondadhesive interlayers 706, 712 are configured to keep the laminatedstructure 702 together even when shattered/broken, and prevent thelaminated structure 702 from breaking up into large, sharp pieces.

As additionally shown in the embodiment of FIG. 7 , the first substrate710, the first adhesive interlayer 706, the electrochromic film 704, thesecond adhesive interlayer 712, and the second substrate 716 may eachhave about an equal width as one another, as well as about an equalheight as one another; however, this need not be the case in otherembodiments.

As further shown in FIG. 7 , the module 700 includes a support unit 718(e.g., a frame) having an interior region 720. The interior region 720of the support unit 718 may be configured to fasten/attach/secure one ormore peripheral portions 722 of the laminated structure 702, therebyproducing the complete module 700. As discussed above, one or moreelectrical components configured to control operation of theelectrochromic film 704 may be disposed within the support unit 718,e.g., disposed in an area located between the interior region 720 and anexterior region 724 of the support unit 718.

A simplified schematic of the module 700 of FIG. 7 installed as aninterior window of an exterior window structure is shown in FIG. 8 ,according to one exemplary embodiment. For clarity purposes only, thevarious components of FIG. 8 (e.g., exterior window, module, etc.) areshown spaced apart.

As shown in FIG. 8 , an exterior window structure 802 may include anexterior window 804, the peripheral portions of which areattached/secured to an inner region 806 of an exterior window frame 808.As further shown in FIG. 8 , the module 700 may be positioned adjacentto, in spaced relation with, in contact with, etc., the inner surface810 of the exterior window 804. One or more peripheral portions 812 ofthe module 700 may also be attached/secured to the interior region 806of the exterior window frame 808.

Integration of an Electrochromic Film into a Structure Comprising Low-eGlass

Low-emissivity (“low-e”) glass is a type of energy-efficient glassdesigned to reduce heat transfer between the environments located oneither side thereof (e.g., between the interior of a room and theoutside/outdoors). Window glass is highly thermally emissive by nature.Accordingly, to improve thermal insulation and solar optical control,specific thin-film coatings are deposited on the glass surface. Low-ecoatings have been developed to minimize the amount of ultraviolet andinfrared light that can pass through glass without compromising theamount of visible light that is transmitted. The low-e coating is amicroscopically thin, transparent coating, which reflects long-waveinfrared energy (or heat). Some low-e coatings also reflect significantamounts of short-wave solar infrared energy. To protect the low-ecoating, an insulated double glazing structure may be utilized as shownin FIG. 9 , according to one exemplary embodiment.

As shown in FIG. 9 , the double glazing structure 900 includes a firstpanel 902 having a first surface 904 and second surface 906. Per theexemplary embodiment of FIG. 9 , the first surface 904 of the firstpanel 902 faces towards, and is in contact with, an exterior environment(e.g., the outside), thus the first panel 902 may also be referred to asthe exterior panel. In certain embodiments, the first panel 902 maycomprise a transparent substrate, such as transparent glass. In variousembodiments, the first panel 902 may comprise a rigid (non-pliant)material; a semi-rigid (semi-pliant) material; a pliant/flexiblematerial, and combinations thereof.

The double glazing structure 900 additionally includes a second panel908 in parallel, spaced relation with the first panel 902. The secondpanel 908 includes a third surface 910 and a fourth surface 912. Per theexemplary embodiment of FIG. 9 , the fourth surface 912 of the secondpanel 902 faces towards, and is in contact with, an interior environment(e.g., the interior of a room), thus the second panel 908 may also bereferred to as the interior panel. The third surface 910 of the secondpanel 908 faces toward the second surface 906 of the first panel 902. Incertain embodiments, the second panel 908 may comprise a transparentsubstrate, such as transparent glass. In various embodiments, the secondpanel 908 may comprise a rigid (non-pliant) material; a semi-rigid(semi-pliant) material; a pliant/flexible material, and combinationsthereof.

A spacer 914 may be positioned between the first and second panels 902,908. The spacer 914 may include a polymer material, an insulatingmaterial, or other material suitable to separate panels in a doubleglazing structure as would be appreciated by skilled artisans uponreading the present disclosure.

The double glazing structure 900 may also include one or more supportunits 916 configured to secure/attach the first panel 902, the secondpanel 908, the spacer 914, and/or other components of the structure 900.

A low-e coating 918 may be deposited on one more surfaces of the firstand/or second panels 902, 908 of the double glazing structure 900. Inthe exemplary embodiment of FIG. 9 , a low-e coating 918 is deposited onthe second surface 906 of the first panel 902. However, the position ofthe low e-coating 918 is not limited to the second surface 906 of thefirst panel 902. For instance, in some embodiments, a low e-coating 918may be deposited on the third surface 910 of the second panel 908. Inadditional embodiments, a first low-coating 918 may be deposited on thesecond surface 906 of the first panel 902, and a second low-e coating918 may be deposited on the third surface 910 of the second panel 908.

In some embodiments, the low-e coating 918 may be a sputtered multilayercoating comprising metals, metals oxides, and/or metal nitrides. In oneembodiment, at least one of the layers of such a sputtered multilayercoating may comprise silver. In some embodiments, the low-e coating 918may be a pyrolytic coating comprising one or more metal oxides (e.g.,SnO₂).

In embodiments where the double glazing structure 900 comprises at leasttwo low-e coatings 918, the coatings may have the same or differentcomposition, optical properties, dimensions, etc. as one another.

As discussed in greater detail below, the double glazing structure 900may comprise an electrochromic film (not shown in FIG. 9 ) deposited onone or more surfaces of the first and/or second panels 902, 908 (e.g.,the first surface 904, the second surface 906, the third surface 910and/or the fourth surface 912), in some embodiments. This electrochromicfilm preferably comprises a solid state electrolyte disposed therein. Inadditional embodiments, the first panel 902 and/or the second panel 908of the double glazing structure 900 may comprise a laminated structurehaving an electrochromic film therein. In more embodiments, the doubleglazing structure 900 may include an electrochromic film positionedbetween the first and second panels 902, 908, where the first panel 902,the electrochromic film, and the second panel 908 are in spaced relationwith each other (i.e., the first panel 902, the electrochromic film, andthe second panel 908 do not come into physical contact with oneanother).

A. Double Glazing Structure in which at Least One Panel Includes aLaminated Structure with an Electrochromic Film Therein

FIGS. 10A-10F illustrate cross-sectional views of a double glazingstructure 1000 in which at least one of the panels includes a laminatedstructure with an electrochromic film disposed therein, and where theelectrochromic film comprises a solid state electrolyte disposedtherein, according to various exemplary embodiments. The double glazingstructure 1000 of FIGS. 10A-10F may be implemented in combination withother devices/features/components described herein, such as thosedescribed with reference to other embodiments. The double glazingstructure 1000 may also be used in various applications and/or inpermutations, which may or may not be noted in the illustrativeembodiments/aspects described herein. For instance, the double glazingstructure 1000 may include more or less features/components than thoseshown in FIGS. 10A-10F, in some embodiments. Additionally, unlessotherwise specified, one or more components of the double glazingstructure 1000 may be of conventional material, design, and/orfabricated using known techniques, as would be appreciated by skilledartisans upon reading the present disclosure.

The double glazing structure 1000 of FIGS. 10A-10F is directed to anexemplary variation of the double glazing structure 900 of FIG. 9 , andthus may have common numbering therewith. For instance, as shown inFIGS. 10A-10F, the double glazing structure 1000 includes: a first panel902 having first and second surfaces 904, 906; a second panel 908 havingthird and fourth surfaces 910, 912; a spacer 914 separating the firstand second panels 902, 908; one or more support units 916 configured tosecure/attach one or more components of the structure 1000; and a low-ecoating 918 deposited on at least one surface of at least one panel.

Referring first to the embodiment of FIG. 10A, the double glazingstructure 1000 includes the first panel 902 and the second panel 908,where the first panel 902 has a laminated structure 1002 with anelectrochromic film 1004 therein. The laminated structure 1002 comprisesa first adhesive interlayer 1006 interposed between the electrochromicfilm 1004 and a first substrate 1008, and a second adhesive interlayer1010 interposed between the electrochromic film 1004 and a secondsubstrate 1012. In certain embodiments, this laminated structure 1002may be formed according to the method 300 of FIG. 3 , and have asimilar, or the same, configuration and/or composition of the structure500 of FIG. 5 . Additionally, the electrochromic film 1004 may comprisea solid state electrolyte disposed therein, in some embodiments.

As also shown in the embodiment of FIG. 10A, the low-e coating 918 maybe deposited on the second surface 906 of the first panel 902, whichcoincides with the inwardly facing surface of the second substrate 1012.However, in another exemplary embodiment, the low-e coating 918 may bedeposited on the third surface 910 of the second panel 908, as shown inFIG. 10B. In still another exemplary embodiment, a first low-e coating918 may be deposited on the second surface 906 of the first panel 902,and a second low-e coating 918 may be deposited on the third surface 910of the second panel 908, as shown in FIG. 10C.

FIGS. 10D-10F illustrate embodiments in which the second panel 908 ofthe double glazing structure 1000 has the laminated structure 1002 withthe electrochromic film 1004 therein. The low-e coating 918 may bedeposited on the second surface 906 of the first panel 902 (as shown inFIG. 10D), the third surface 910 of the second panel 908 (as shown inFIG. 10E), or on both the second surface 906 of the first panel 902 andthe third surface 910 of the second panel 908 (as shown in FIG. 10F).

The double glazing structure 1000 illustrated in FIGS. 10A-10F includestwo panels 902, 908, where at least one of the panels includes alaminated structure 1002 with an electrochromic film 1004 disposedtherein. The use of such a laminated structure with an electrochromicfilm disposed therein may also be applicable to glazing structureshaving any number of panels, such as those having more than two panels,in certain embodiments.

While not shown in FIGS. 10A-10F, the first panel 902 may have a firstlaminated structure 1002 with an electrochromic film 1004 therein, andthe second panel 908 may have a second laminated structure 1002 with anelectrochromic film 1004 therein, in some embodiments. In one suchembodiment in which each of the panels 902, 908 have a laminatedstructure 1002 with an electrochromic film 1004 therein, a low e-coating918 may be deposited on the second surface 906 of the first panel 902.In another such embodiment in which each of the panels 902, 908 have alaminated structure 1002 with an electrochromic film 1004 therein, a lowe-coating 918 may be deposited on the third surface 910 of the secondpanel 908. In yet another such embodiment in which each of the panels902, 908 have a laminated structure 1002 with an electrochromic film1004 therein, a first low e-coating 918 may be deposited on the secondsurface 906 of the first panel 902, and a second low e-coating 918 maybe deposited on the third surface 910 of the second panel 908.

B. Double Glazing Structure Having an Electrochromic Film Deposited onat Least One Surface of at Least One Panel

FIGS. 11A-11H illustrate cross-sectional views of a double glazingstructure 1100 in which at least one of the panels includes a laminatedstructure with an electrochromic film disposed therein, and where theelectrochromic film comprise a solid state electrolyte disposed therein,according to various exemplary embodiments. The double glazing structure1100 of FIGS. 11A-11H may be implemented in combination with otherdevices/features/components described herein, such as those describedwith reference to other embodiments. The double glazing structure 1100may also be used in various applications and/or in permutations, whichmay or may not be noted in the illustrative embodiments/aspectsdescribed herein. For instance, the double glazing structure 1100 mayinclude more or less features/components than those shown in FIGS.11A-11H, in some embodiments. Additionally, unless otherwise specified,one or more components of the double glazing structure 1100 may be ofconventional material, design, and/or fabricated using known techniques,as would be appreciated by skilled artisans upon reading the presentdisclosure.

The double glazing structure 1100 of FIGS. 11A-11H is directed to anexemplary variation of the double glazing structure 900 of FIG. 9 , andthus may have common numbering therewith. For instance, as shown inFIGS. 11A-11H, the double glazing structure 1100 includes: a first panel902 having first and second surfaces 904, 906; a second panel 908 havingthird and fourth surfaces 910, 912; a spacer 914 separating the firstand second panels 902, 908; one or more support units 916 configured tosecure/attach one or more components of the structure 1100; and a low-ecoating 918 deposited on at least one surface of at least one panel.

As particularly shown in the embodiments of FIGS. 11A-11C, the doubleglazing structure 1100 may include the low-e coating 918 deposited onthe second surface 906 of the first panel 902. An electrochromic film1102 may also be deposited on the third surface 910 of the second panel908 (as shown in FIG. 11A), the fourth surface 912 of the second panel908 (as shown in FIG. 11B), or on the first surface 904 of the firstpanel 902 (as shown in FIG. 11C).

As further shown in the embodiments of FIGS. 11D-11F, the double glazingstructure 1100 may include the low-e coating 918 deposited on the thirdsurface 910 of the second panel 909. An electrochromic film 1102 mayalso be deposited on the second surface 906 of the first panel 902 (asshown in FIG. 11D), the fourth surface 912 of the second panel 908 (asshown in FIG. 11E), or on the first surface 904 of the first panel 902(as shown in FIG. 11F).

As additionally shown in the embodiments of FIGS. 11G-11H, the doubleglazing structure 1100 may include a first low-e coating 918 depositedon the second surface 906 of the first panel 902, and a second low-ecoating 918 deposited on the third surface 910 of the second panel 909.An electrochromic film 1002 may also be deposited on the fourth surface912 of the second panel 908 (as shown in FIG. 11G), or on the firstsurface 904 of the first panel 902 (as shown in FIG. 11H).

In certain embodiments, the electrochromic film 1102 of FIGS. 11A-11Gmay be deposited on a particular panel surface of the double glazingstructure 1102 via the method 100 described in FIG. 1 .

C. Double Glazing Structure in which an Electrochromic Film is DisposedBetween, and not in Physical Contact with, Two Panels

FIG. 12 illustrates a double glazing structure 1200 having at least twopanels, and an electrochromic film disposed between, and not in physicalcontact with, the two panels, where the electrochromic film comprises asolid state electrolyte disposed therein. The double glazing structure1200 of FIG. 12 may be implemented in combination with otherdevices/features/components described herein, such as those describedwith reference to other embodiments. The double glazing structure 1200may also be used in various applications and/or in permutations, whichmay or may not be noted in the illustrative embodiments/aspectsdescribed herein. For instance, the double glazing structure 1200 mayinclude more or less features/components than those shown in FIG. 12 ,in some embodiments. Additionally, unless otherwise specified, one ormore components of the double glazing structure 1200 may be ofconventional material, design, and/or fabricated using known techniques,as would be appreciated by skilled artisans upon reading the presentdisclosure.

The double glazing structure 1200 of FIG. 12 is directed to an exemplaryvariation of the double glazing structure 900 of FIG. 9 , and thus mayhave common numbering therewith. For instance, as shown in FIG. 12 , thedouble glazing structure 1200 includes: a first panel 902 having firstand second surfaces 904, 906; a second panel 908 having third and fourthsurfaces 910, 912; one or more support units 916 configured tosecure/attach one or more components of the structure 1000; and a low-ecoating 918 deposited on at least one surface of at least one panel.

Moreover, as also shown in FIG. 12 , the double glazing structure 1200may include a central panel 1202 having an electrochromic filmassociated therewith, where the central panel (and associatedelectrochromic film) is positioned between the first and second panels904, 908 in a configuration that prevents the central panel 1202 (andassociated electrochromic film) from coming into physical contact withthe first and second panels 904, 908. The central panel 1202 may beseparated from the first panel 902 by a first distance, d₁, andseparated from the second panel 908 by a second distance, d₂, where d₁and d₂ may or may not be equal. In some embodiments, the region 1204between the central panel 1202 and the first panel 902, and/or theregion 1206 between the central panel 1202 and the second panel 908, maybe comprised of dry air, N₂, Argon, or other insert gas, as would beappreciated by skilled artisans upon reading the present disclosure.

In some embodiments, the central panel 1202 may include a laminatedstructure having the electrochromic film disposed therein. Such alaminated structure may be formed via the method 300 of FIG. 3 , and/orhave the configuration, composition, etc. of the laminated structure 500of FIG. 5 .

In some embodiments, the central panel 1202 may include a substrate(e.g., a transparent glass substrate) having the electrochromic filmdeposited on a surface thereof. In one such embodiment, theelectrochromic film may be deposited on the surface of the substratethat faces toward the first panel 902. In another such embodiment, theelectrochromic film may be deposited on the surface of the substratethat faces toward the second panel 908. In various embodiments, theelectrochromic film may be deposited/adhered/laminated on the substratevia the method 100 of FIG. 1 .

In some embodiments, the central panel 1202 may be comprised solely ofthe electrochromic film.

In the embodiment shown in FIG. 12 , the low e-coating 918 is depositedon the second surface 906 of the first panel 902. However, in anotherembodiment, the low e-coating 918 may be deposited on the third surface910 of the second panel 908. In yet another embodiment, a firstlow-coating 918 may be deposited on the second surface 906 of the firstpanel 902, and a second low-e coating 918 may be deposited on the thirdsurface 910 of the second panel 908. Regardless of the position of thelow-e coating 918 (e.g., on the second surface 906 of the first panel902, on the third surface 910 of the second panel 908, or on both thesecond surface 906 of the first panel 902 and the third surface 910 ofthe second panel 908), the central panel 1202 may include theelectrochromic film in any of the configurations disclosed herein (e.g.,the central panel 1202 comprising solely the electrochromic film, thecentral panel 1202 comprising the electrochromic film deposited directlyon a surface of a substrate, or the central panel 1202 comprising alaminated structure with the electrochromic film disposed therein).

Electrochromic Film

An exemplary, non-limiting schematic of an electrochromic film 1300comprising a solid electrolyte disposed therein is shown in FIG. 13 ,according to one embodiment. It is important to note that theelectrochromic film 1300 of FIG. 13 may be implemented in combinationwith other devices/features/components described herein, such as thosedescribed with reference to other embodiments/aspects. Theelectrochromic film 1300 may be used in various applications and/or inpermutations, which may or may not be noted in the illustrativeembodiments/aspects described herein. For instance, the electrochromicfilm 1300 may include more or less features/components than those shownin FIG. 13 , in some embodiments. Additionally, unless otherwisespecified, one or more components of the electrochromic film 1300 may beof conventional material, design, and/or fabricated using knowntechniques (e.g., sputtering, chemical vapor deposition (CVD), physicalvapor deposition (PVD), plasma-enhanced chemical vapor deposition(PECVD), spray coating, slot-die coating, dip coating, spin coating,printing, etc.), as would be appreciated by skilled artisans uponreading the present disclosure.

As shown in FIG. 13 , the electrochromic film 1300 includes a firsttransparent substrate 1302 and a second transparent substrate 1304 inspaced, parallel relation with one another. The first and secondsubstrates 1302, 1304 may have the same or different dimensions,comprise the same or different material, etc. Suitable material for thefirst substrate 1302 and/or the second substrate 1304 may include, butis not limited to, glass, polymeric materials, plastic materials, and/orother materials which are transparent in at least part of the visibleregion of the electromagnetic spectrum. In some embodiments, the firstand second substrates 1302, 1304 may comprise glass.

As also shown in FIG. 13 , a first transparent electrically conductivefilm 1306 is deposited on the interior surface 1308 of the firstsubstrate 1302 to act as an electrode. A second transparent electricallyconductive film 1310 is also deposited on the interior surface 1312 ofthe second substrate 1304 to act as electrode. The first and secondelectrically conductive films 1306, 1310 may have the same or differentdimensions, comprise the same or different material, etc. The first andsecond electrically conductive films 1306, 1310 may also eachindependently have a single layer or multilayer structure. Suitablematerial for the first and second electrically conductive films 1306,1310 may include, but is not limited to, tin doped indium oxide (ITO),fluorine doped indium oxide, antimony doped indium oxide, zinc dopedindium oxide, aluminum doped zinc oxide, silver nano wire, metal mesh,combinations thereof, and/or other such transparent material exhibitingsufficient electrical conductance. In preferred aspects, the first andsecond electrically conductive films 1306, 1310 may comprise ITO.

The electrochromic device 1300 may additionally include an electricalpower supply (not shown) configured to supply voltage between the firstand second electrically conductive films 1306, 1310.

As further shown in FIG. 13 , a layer 1314 of electrochromic material isdeposited on the interior surface 1316 of the first electricallyconductive film 1306. The layer 1314 of electrochromic material isconfigured to effect a reversible color change upon reduction (gain ofelectrons) or oxidation (loss of electron) caused by exposure to anelectrical current. In some embodiments, the layer 1314 ofelectrochromic material may be configured to change from a transparentstate to a colored state, or from a colored state to another coloredstate, upon oxidation or reduction. In some embodiments, the layer 1314of electrochromic material may be a polyelectrochromic material in whichmore than two redox states are possible, and may thus exhibit severalcolors.

In some embodiments, the layer 1314 of electrochromic material maycomprise an organic electrochromic material, an inorganic electrochromicmaterial, a mixture of both, etc. The layer 1314 of electrochromicmaterial may also be a reduction colored material (i.e., a material thatbecomes colored upon acquisition of electrons), or an oxidation coloredmaterial (i.e., a material that becomes colored upon the loss ofelectrons).

In some embodiments, the layer 1314 of electrochromic material mayinclude a metal oxide such as MoO₃, V₂O₅, Nb₂O₅, WO₃, TiO₂, Ir(OH)_(x),SrTiO₃, ZrO₂, La2O₃, CaTiO₃, sodium titanate, potassium niobate,combinations thereof, etc. In some embodiments, the layer 1314 ofelectrochromic material may include a conductive polymer such aspoly-3,4-ethylenedioxy thiophene (PEDOT), poly-2,2′-bithiophene,polypyrrole, polyaniline (PANT), polythiopene, polyisothianaphthene,poly(o-aminophenol), polypyridine, polyindole, polycarbazole,polyquinone, octacyanophthalocyanine, combinations thereof, etc.Moreover, in some embodiments, the layer 1314 of electrochromic materialmay include materials, such as viologen, anthraquinone, phenocyazine,combinations thereof, etc. Additional examples of electrochromicmaterials, particularly those including multicolored electrochromicpolymers, may be found in U.S. Patent Application No. 62/331,760, filedMay 4, 2016, the entirety of which is herein incorporated by reference.

As additionally shown in FIG. 13 , a charge storage layer 1318 isdeposited on the interior surface 1320 of the second electricallyconductive film 1310. Suitable materials for the charge storage layer1318 may include, but are not limited to, vanadium oxide, binary oxides(e.g., CoO, IrO₂, MnO, NiO, and PrO_(x)), ternary oxides (e.g.,Ce_(x)V_(y)O_(z)), etc.

In some embodiments, the charge storage layer 1318 may be replaced withan optional second layer of electrochromic material. This optionalsecond layer of electrochromic material may have the same or differentdimensions, comprise the same or different composition, etc., as thefirst layer 1314 of electrochromic material.

The electrochromic device 1300 also includes an electrolyte layer 1322positioned between the layer 1314 of electrochromic material and thecharge storage layer 1318. In some embodiments, the electrolyte layer1322 may include a liquid electrolyte as known in the art. In someembodiments, the electrolyte layer 1322 may include a solid stateelectrolyte, including but not limited to, Ta₂O₅, MgF, Li₃N, LiPO₄,LiBO₂—Li₂SO₄, etc. In some embodiments, the electrolyte layer 1322 mayinclude a polymer based electrolyte comprising an electrolyte salt(e.g., LiTFSI, LiPF₆, LiBF₄, LiClO₄, LiCF₃SO₃, LiN(CF₃SO₂)₂, LiSbFg,LiAsF₆, LiN(CF₃CF₂SO₂)₂, (C₂H₅)₄NBF₄, (C₂H₅)₃CH₃NBF₄, LiI, etc.), apolymer matrix (e.g., polyethylene oxide, poly(vinylidenefluoride(PVDF), poly(methyl methacrylate) (PMMA), polyethylene oxide(PEO), poly(acrylonitrile) (PAN), polyvinyl nitrile, etc.), and one ormore optional plasticizers (e.g., glutaronitrile, succinonitrile,adiponitrile, fumaronitrile, etc.).

In some embodiments, the electrolyte layer 1322 comprises a solidpolymer electrolyte. In one embodiment, the solid polymer electrolytecomprises a polymer framework, at least one solid plasticizer, and atleast one electrolyte salt. In some embodiments, the polymer frameworkmay include a polar polymer material having an average molecular weightof about 10,000 Daltons or greater. In particular embodiments, the polarpolymer material may have an average molecular weight in a range fromabout 10,000 Daltons to about 800,000,000 Daltons. In some embodiments,the polar polymer material may be present in an amount ranging fromabout 15 wt. % to about 80 wt. % based on the total weight of the solidpolymer electrolyte.

The aforementioned polar polymer material may include one or more polarpolymers, each of which may include one or more of: C, N, F, O, H, P, F,etc. Suitable polar polymers may include, but are not limited to,polyethylene oxide, poly(vinylidene fluoride-hexafluoropropylene,poly(methyl methacrylate), polyvinyl nitrile, combinations thereof, etc.In embodiments where a plurality of polar polymers is present, thepolymers may be crosslinked to form a network having enhanced mechanicalproperties.

The polar polymer material may have a sufficient amorphicity so as toachieve sufficient ion conductivity. Amorphous polymer materialstypically exhibit high ion conductivities. Accordingly, in someembodiments, the polar material disclosed herein may have an amorphous,or a substantially amorphous, microstructure.

In some embodiments, the polar polymer material may have asemi-crystalline or crystalline microstructure. In such cases, variousmodifications may be implemented with respect to the polymer material tosuppress the crystallinity thereof. For instance, one modification mayinvolve use of branched polar polymers, linear random copolymers, blockcopolymers, comb polymers, and/or star-shaped polar polymers. Anothermodification may include incorporation of an effective amount of solidplasticizers in the polar polymer material, as discussed in greaterdetail below.

Various properties of the polar polymer material also may be selectedand/or modified to maximize ion conductivity. These properties mayinclude, but are not limited to, glass transition temperature, segmentalmobility/flexibility of the polymer backbone and/or any side chainsattached thereto, orientation of the polymers, etc.

As noted above, the presently disclosed solid electrolyte may include atleast one solid plasticizer. The at least one solid plasticizer may besubstantially miscible in the polymer framework of the solidplasticizer. The at least one solid plasticizer may include an organicmaterial (e.g., small, solid organic molecules) and/or an oligomericpolymer material, in some embodiments. In various embodiments, the atleast one solid plasticizer may be selected from the group includingglutaronitrile, succinonitrile, adiponitrile, fumaronitrile, andcombinations thereof.

In some embodiments, a plurality of solid plasticizers may be present inthe polymer framework, where each plasticizer may independently includean organic material (e.g., small, solid organic molecules) and/or anoligomeric polymer material. Particularly, each plasticizer mayindependently be glutaronitrile, succinonitrile, adiponitrile,fumaronitrile, etc. Moreover, the dimensions of at least two, some, amajority, or all of the plasticizers may be the same or different as oneanother.

In some embodiments, the total amount of solid plasticizer may be in arange from about 20 wt. % to about 80 wt. % based on the total weight ofthe solid electrolyte.

As additionally noted above, the solid polymer electrolyte may includeat least one electrolyte salt. In some embodiments, the at least oneelectrolyte salt may comprise an organic salt. In some embodiments, theat least one electrolyte salt may comprise an inorganic salt. Suitableelectrolyte salts may include, but are not limited to, LiTFSI, LiPF₆,LiBF₄, LiClO₄, LiCF₃SO₃, LiN(CF₃SO₂)₂, LiSbFg, LiAsF₆, LiN(CF₃CF₂SO₂)₂,(C₂H₅)₄NBF₄, (C₂H₅)₃CH₃NBF₄, LiI, combinations thereof, etc. In someembodiments, the total amount of electrolyte salt may be in a range fromabout 10 wt. % to about 50 wt. % based on the total weight of the solidelectrolyte.

The solid polymer electrolyte is distinguishable from conventionalliquid electrolytes, as well as gel polymer electrolytes including anionic liquid therein. In other words, the presently disclosed solidpolymer electrolyte may be an all solid polymer electrolyte, and doesnot include any liquid or gel components therein. The presentlydisclosed solid polymer electrolyte may also be transparent in someaspects. Additionally, the solid polymer electrolyte may have an ionconductivity in a range from about 10⁻⁷ S/cm to about 10⁻³ S/cm.

Methods of making the presently disclosed solid polymer electrolyte mayinclude synthesis, polymerization, solvation, etc. processes as known inthe art. In one particular, non-limiting embodiment, a method of makingthe presently disclosed polymer electrolyte may include: (a) combiningthe polymer framework, the at least one plasticizer, and the at leastone electrolyte salt in an appropriate solvent; and (b) removing thesolvent to obtain the solid polymer electrolyte. Exemplary solvents mayinclude, but are not limited to, acetone, methanol, tetrahydrofuran,etc. In some embodiments, one or more experimental parameters may beoptimized to facilitate the dissolving of the polymer framework,plasticizer, and electrolyte salt in the solvent. These experimentalparameters may include the components remain in the solvent,agitation/stirring of the solvent, etc.

In some embodiments, the electrolyte layer 1322 of FIG. 13 comprises asolid polymer electrolyte, such as the solid polymer electrolytesdescribed above, and does not include any liquid or gel electrolyte.Such a solid polymer electrolyte (i) has sufficient mechanical strengthyet is versatile in shape so as to allow easy formation into thin films,and thin-film shaped products; (ii) avoids issues related to adhesionand print processing affecting conventional electrolytes; (iii) providesstable contact between the electrolyte/electrode interfaces (those withand without the electrochromic material coating thereon); (iv) avoidsthe problem of leakage commonly associated with liquid electrolytes; (v)has desirable non-toxic and non-flammable properties; (vi) avoidsproblems associated with evaporation due to its lack of vapor pressure;(vii) exhibits improved ion conductivities as compared to conventionpolymer electrolytes; etc.

Additional examples of electrolyte materials, particularly thoseincluding solid polymer electrolytes, may be found in U.S. PatentApplication No. 62/323,407, filed Apr. 15, 2016, the entirety of whichis herein incorporated by reference.

EXAMPLES 1. Electrochromic Film Laminated Directly on a Glass Substrate

An electrochromic film was fabricated in the configuration of:PET/ITO/Electrochromic Layer/Solid State Electrolyte Layer/ChargeStorage Layer/ITO/PET. The basic structure of the electrochromic film isprovided in FIG. 13 . Both the bottom electrode and the top electrode ofthe electrochromic film are flexible PET/ITO films. The sheet resistanceof the film ranges from 1 Ω/sq to 200 Ω/sq. The transmission of the filmranges from 95% to 10%.

Fabrication of the electrochromic film involved depositing theelectrochromic layer and the solid state electrolyte in sequence on thebottom electrode using slot-die coating. The charge storage layer wasdeposited on the top electrode using slot-die coating. Subsequently, thebottom electrode and the top electrode were laminated together.

To laminate the electrochromic film directly onto the glass, the glass'ssurface was first thoroughly cleaned. Following the process described inmethod 100 of FIG. 1 , the electrochromic film was laminated onto theglass.

FIG. 14 provides a schematic representation of the resulting structurecomprising the glass substrate 1402 with the electrochromic film 1404laminated directly thereon.

2. Laminated Glass Structure with an Electrochromic Film DisposedTherein

The electrochromic film comprising a solid state electrolyte therein wasfabricated as disclosed in Example 1. To laminate the electrochromicfilm inside two glass panels, the electrochromic film was interposed(sandwiched) between two EVA adhesive interlayers, and placed betweentwo glass panels. The assembly was put inside a vacuum oven to bake at125° C. for 30 minutes.

FIG. 15 provides a schematic representation of the resulting laminatedglass structure comprising the two glass panels 1502, 1504 and theelectrochromic film 1506 therebetween.

3. Smart Window Module Comprising a Laminated Glass Structure with anElectrochromic Film Disposed Therein

Laminated glass with an electrochromic film inside was fabricated asdescribed in Example 2. Subsequently, the laminated glass having theelectrochromic film inside was integrated with a frame to function as asmart window module.

FIGS. 16A-16B provide schematic representations of the resulting smartwindow module comprising the support unit 1602, and the laminated,transparent glass structure 1604 having the electrochromic film inside.As particularly shown in FIG. 16A-16B, the electrochromic film is in atransparent state and an opaque state, respectively, as indicated by thedifferent stippling patterns.

4. Formation of a Solid Polymer Electrolyte Configured for Use in anElectrochromic Film

An exemplary solid polymer electrolyte as discussed herein was preparedas follows.

The following components were combined: 40 wt. % PEO having a molecularweight of 1,000,000; 10 wt. % PEO having a molecular weight of 1,500; 30wt. % succinonitrile; and 20 wt. %, LiClO₄. The combined components weremixed in an acetone solvent and stirred overnight to obtain a solution.The solution was processed and deposited on a PEDOT-PSS electrochromiclayer via spin-coating, dip-coating, drop-casting, blade coating, screenprinting, etc. After drying the solvent, the resulting solid electrolytewas found to be transparent with an ion conductivity of about 10⁻⁴ S/cm.

An electrochromic film was formed comprising a first transparentITO-coated glass electrode on which the PEDOT-PESS electrochromic layerwas deposited, as well as a second transparent ITO-coated glasselectrode, where the solid electrolyte was located/sandwiched betweenthe transparent ITO/PEDOT-PSS layers and the second transparent ITOglass layer. This particular electrochromic device was found to switchto a blue color at 5 V, and switch back to colorless at −2 V.

APPLICATIONS/USES

Embodiments of the methods and systems disclosed herein may be used invarious applications, devices, industries etc. For instance, severalexemplary methods for integrating one or more electrochromic films ontoand/or within a substrate structure have been presented herein. Suchmethods allow for a low cost, reproducible, and convenient process bywhich an end user may integrate the electrochromic film(s) with adesired substrate structure. Applications for such methods and theresulting products include, but are not limited to smart window anddisplay technology, e.g., anti-glare car mirrors, smart windowsconfigured to modulate the transmission or reflected solar radiation foruse in cars, aircrafts, buildings, and the like; protective eyewear;camouflage and/or chameleonic materials; polymer photovoltaic devices;field effect transistors; batteries; supercapacitors; light emittingdiodes; and other electrochromic and electronic devices.

The invention described and claimed herein is not to be limited in scopeby the specific preferred embodiments disclosed herein, as theseembodiments are intended as illustrations of several aspects of theinvention. Indeed, various modifications of the invention in addition tothose shown and described herein will become apparent to those skilledin the art from the foregoing description. Such modifications are alsointended to fall within the scope of the appended claims.

What is claimed is:
 1. An electrochromic device comprising: anelectrochromic film that comprises: a first electrochromic layer; asolid state electrolyte; and a second electrochromic layer separatedfrom the first electrochromic layer by the solid state electrolyte,wherein: the solid state electrolyte layer contacts the firstelectrochromic layer at a first contacting surface and contacts thesecond electrochromic layer at a second contacting surface; a firstconductive layer disposed adjacent to the first electrochromic layer andon an opposing surface to the first contacting surface; a secondconductive layer disposed adjacent to the second electrochromic layerand on an opposing surface to the second contacting surface; and thefirst electrochromic layer is configured to (1) switch to a coloredstate upon application of a threshold voltage between the firstconductive layer and the second conductive layer, and (2) switch to acolorless state upon application of a second negative threshold voltagebetween the first conductive layer and the second conductive layer,wherein an absolute value of the second negative threshold voltage isdifferent from an absolute value of the threshold voltage.
 2. Theelectrochromic device of claim 1, wherein the solid state electrolytecomprises: an electrolyte salt selected from the group of LiTFSI, LiPF₆,LiBF₄, LiClO₄, LiCF₃SO₃, LiN(CF₃SO₂)₂, LiSbFg, LiAsF₆, LiN(CF₃CF₂SO₂)₂,(C₂H₅)₄NBF₄, (C₂H₅)₃CH₃NBF₄, and LiI; and a polymer matrix comprisingone or more polar polymers that comprise a semi-crystalline orcrystalline microstructure.
 3. The electrochromic device of claim 1,wherein the first conductive layer contacts the first electrochromiclayer at a third contacting surface and the second conductive layercontacts the second electrochromic layer at a fourth contacting surface;and the electrochromic film further comprises: a first substratedisposed adjacent to the first conductive layer and on an opposingsurface to the third contacting surface; and a second substrate disposedadjacent to the second conductive layer and on an opposing surface tothe fourth contacting surface.
 4. The electrochromic device of claim 1,wherein at least one of the first electrochromic layer and the secondelectrochromic layer comprises more than two differently colored statesdepending on an amount or concentration of electrons.
 5. Theelectrochromic device of claim 1, further comprising an adhesive layerinterposed between the electrochromic film and an external substrate. 6.The electrochromic device of claim 5, wherein the adhesive layer isconfigured to cross-link the electrochromic film to the externalsubstrate.
 7. A method for forming an electrochromic film of anelectrochromic device, the method comprising: interposing a solid stateelectrolyte between a first electrochromic layer and a secondelectrochromic layer by contacting the first electrochromic layer to thesolid state electrolyte at a first contacting surface and contacting thesecond electrochromic layer to the solid state electrolyte at a secondcontacting surface; inserting, on an opposing surface to the firstcontacting surface, a first conductive layer; inserting, on an opposingsurface to the second contacting surface, a second conductive layer,wherein: the first electrochromic layer is configured to (1) switch to acolored state upon application of a threshold voltage between the firstconductive layer and the second conductive layer, and (2) switch to acolorless state upon application of a second negative threshold voltagebetween the first conductive layer and the second conductive layer,wherein an absolute value of the second negative threshold voltage isdifferent from an absolute value of the threshold voltage.
 8. The methodof claim 7, wherein the solid state electrolyte comprises: anelectrolyte salt selected from the group of LiTFSI, LiPF₆, LiBF₄,LiClO₄, LiCF₃SO₃, LiN(CF₃SO₂)₂, LiSbFg, LiAsF₆, LiN(CF₃CF₂SO₂)₂,(C₂H₅)₄NBF₄, (C₂H₅)₃CH₃NBF₄, and LiI; and a polymer matrix comprisingone or more polar polymers that comprise a semi-crystalline orcrystalline microstructure.
 9. The method of claim 7, wherein: theinserting of the first conductive layer comprises contacting the firstelectrochromic layer to the first conductive layer at a third contactingsurface; the inserting of the second conductive layer comprisescontacting the second electrochromic layer to the second conductivelayer at a fourth contacting surface; and the method further comprises:inserting, on an opposing surface to the third contacting surface, afirst substrate; and inserting, on an opposing surface to the fourthcontacting surface, a second substrate.
 10. The method of claim 7,wherein at least one of the first electrochromic layer and the secondelectrochromic layer comprises more than two differently colored statesdepending on an amount or concentration of electrons.
 11. The method ofclaim 7, further comprising: adhering an adhesive layer to be interposedbetween the electrochromic film and an external substrate.
 12. Themethod of claim 11, wherein the adhesive layer cross-links theelectrochromic film to the external substrate.